Basic water-soluble dyestuffs



Patented June 6, 1944 BASIC WATER-SOLUBLE DYESTU FFS BerndgEisterhand Gerd Kochendoerfer, Ludwigshafen-on the-Rhine, Germany; assignors, by mesne assignments, to GeneraLAnilinear Film.-

-, Corporation, NewXork, N. Y., a. ..ecn'poration .o f1

Delaware 7 Noihrawingi Application November I; 1940;.s'e

rial No. 364,676. In Germa'nyxNovmben 27;.

8, Claims. (GI. 260-24 The present invention relates to new basic water-soluble dyestufis of from violet to blue shade.

We have found that styryl dyestuff salts of the general formula cedures set forth in the article by G. Plancher \/\N l which appears in Berichte, v01. 31, (1898) pages (I) 1488 to11499; and irr-particular pages1491, 1496 g and 1497; 'Ilhus; the indolinec derivative withgthe are Very Valuble basic water-soluble dyestuffs, of X substituent in the 5-p0sition'may be prepared.- fromviolet tov blue shade. In that general formuby} a t with, azjphenyli hydrazine having th la the letters R'stand for low-molecular alkyl orre ponding ax substituentin para or 4- groups, Y stands for hydrogen, a-low-molecular h; fi f,h g the'example given b alkyl alkoxyl group z for'the anion of an acid low; one may; start-from the paraor 4.-carboxy-- X for a group containing at least one carbon phenylhydrazine atomidireotly attached to-thelnucleusQmarked Instead of methylene com ound their which carbon atom is boundito'oxygeniormtrocsaltsmaybemsed, asefor example theE-methosulgen by more than one linkage. The group X thus phates, such as are formed by the: addition; of y for e p C0CH8, COC6H5, dialkyl sulphates to the corresponding 2.3;3-tri- 0 6H4 alkylindolenines. CQOCH3, COOC'ZHE, CON(C2H5)2, The new dyestuffs are soluble in water. They The dyestuffs are prepared bycondensing in known manner in an acid medium either an aldehyde of the general formula A (see below) with a 1.3.3 trialkyl-2;-methyleneindoline of. formula 3 By,- or'by" condensing-an aldehyde; of the general;

formulaiC witln a diphenylamine: of the? general formula:-D...,

R R l the same meaning as above. 'Ihe aldehydes-and indol derivatives are prepared according to well known processes.

The indoline derivatives utilized for preparing the dyestuif may be obtained by the same proceduresheretofore.utilized for producing unsubstituted indolines or the 5-methoxy indolines. For example, they may be prepared by applying to the corresponding phenyl hydrazinesthe proare especially usefulim dyeing and printing acetate artificial silk, yielding from violet to blue dyeings of'high brilliancy and intensity, and very fast to water as well as to washing and ironing and to light. The dyestufis are also suitable for dyeing leather, paper, silk and tanned cotton.

' The-:following example=servesito illustrate how thezpresentiiinvention. may.be1car'ried out :in prac:-

ticeg-r. but: the-:- invention: is .notzrestricted to this.

example. j= 'Thezpartsiare; bywweight.

Example .25-=9 -parts of 1-ethy1-2-methylene-3.3-dimeththe solution is filtered oil" from resinous contaminations'and the dyestuif salted out by adding common salt. After filtration by suction and drying a dark bronzing crystal mass is obtained in a good yield which dissolves easily in water and the usual printing pastes. On acetate artificial silk it yields, lear blue-violet .dyeings. and

washing.

prints. oflgpod f astnessto light", andftd Water and r The following table sets forth a series of other combinations as well as the shades obtainable therewith on acetate artificial silk. In these combinations R means CH3 and Y means OC2H52 x: -COOCH3, bluish violet X: -COCH3, bluish violet X: COCsHs, violet blue X: CON(C2H5) 2, violet X: -CN, reddish blue When using, instead of an aldehyde with Y: 1'

like OCzHs, a corresponding aldehyde wherein Y j is hydrogen or alkyl, dyestuffs of a somewhat redder shade are obtained; if one or both of the His attached to the nitrogen atoms shown-in the general Formula I be ethyl, somewhat bluer dye.-

stuffs of otherwise the same constitution are obtained.

:Whatwe claimis: i 1. Basic water-soluble dyestuffs corresponding to the general formula t wherein the letters R stand for low-molecular alkyl-groups, Ystands for a; member'of the'group consisting of hydrogen, lowmolecula'r alkyl and an'goxy group's, Z stands for'the anion of an acid and X stands for a group selected'from the class consisting of the keto, carbox'ylic acid"ester'and amide groups wherein the carbonatom of the carbonyl is directly attached t'o' the" benzene nucleus; I

2; Basic water-soluble dyestuffs corresponding to the general formula 1 wherein the letters R stand-for low-molecular alkyl groups, Y stands for a member of the group consisting of hydrogen, low-molecular alkyl and alkoxy groups, Z standsfor'sthe anion of antacid Y so.

3. Basic water-soluble dyestuffs corresponding to the general formula wherein the letters R stand for low-molecular alkyl groups, Y stands for a member of the group consisting ofhydrogen, low-molecular alkyl and l'alkoxy-group'sj, Z stands for the anion of an acid and Bsta'ndsfor' amember of the group consisting of alkyl and aryl groups.

- 4; Basic water-soluble dyestuffs corresponding to the general formula wherein the letters R stand for low-molecular alkyl groups, Y stands for a member of the;

group consisting of hydrogen; low-molecular alkyl and alkoxy groups, Z stands for the anion of an acid.

I 5. The dyestuff of the formula 6. Basic water-soluble dyestuffs corresponding to the general formula ll R, R alkyl-O-C \C/ wherein the letters R standfor low-molecular alkyl groups, Y stands for a member of the group consisting of hydrogen,,low-molecular alkyl and' Z stands for the anion 'of "an:

alkoxy groups, and

acid.

7. The dyestuff of the formula on; CH;

and X is a kamfitiriaita these the as es atom of the'keto group is attached directly toithe nucleus marked II. i

wherein Z stands for the-anion of an acid.

8. The dyestuff of the formula wherein Z stands for the anion of an acid.

.. BERND EISTERT.

GERDKGCHENDOV mes. 

